Alkylphenyl-substituted group 4 metal complexes, catalysts and olefin polymerization process

ABSTRACT

Group 4 metal complexes of the constrained geometry type, catalysts derived therefrom, and polymerization processes using the same, characterized by an alkaryl-substituted silane bridging group are disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation-in-part of U.S. Ser. No.09/715,380, filed Nov. 17, 2000, which claims benefit of priority fromprovisional applications Nos. 60/170,178, 60/170,177, and 60/170,175,all filed on Dec. 10, 1999.

FIELD OF THE INVENTION

[0002] This invention relates to a class of metal complexes, the ligandsused to prepare these metal complexes, polymerization catalysts derivedtherefrom, and the resulting polymerization processes using the same.More particularly, such metal complexes are characterized by a nitrogencontaining aliphatic or cycloaliphatic moiety that is substituted withone or more aryl groups, an aryl-substituted silane bridging group, orone or more Group 14 organometalloid substituents on the metal.

BACKGROUND

[0003] EP-A-923,589, which is equivalent to WO98/06727, published Feb.19, 1998, disclosed Group 4 metal complexes containing a heteroatomsubstituent at the 3-position of the cyclopentadienyl, especiallyindenyl, ligand groups. Particular heteroatom containing substituentsincluded dihydrocarbylamino substituents including dimethylamino,diethylamino, methylethylamino, methylphenylamino, dipropylamino,dibutylamino, piperidinyl, morpholinyl, pyrrolidinyl,hexahydro-1H-azepin-1-yl, hexahydro-1(2H)-azocinyl,octahydro-1H-azonin-1-yl, and octahydro-1(2H)-azecinyl.

[0004] EP-A-577,581 discloses unsymmetrical bis-Cp metallocenescontaining a fluorenyl ligand with heteroatom substituents. E. Barsties;S. Schaible; M.-H. Prosenc; U. Rief; W. Roll; O. Weyland; B. Dorerer;H.-H. Brintzinger J. Organometallic Chem. 1996, 520, 63-68, and H.Plenio; D. Birth J. Organometallic Chem. 1996, 519, 269-272 disclosesystems in which the cyclopentadienyl ring of the indenyl is substitutedwith a dimethylamino group in non-bridged and Si-bridged bis-indenylcomplexes useful for the formation of isotactic polypropylene andpolyethylene.

[0005] Disclosure of random heteroatom substitution in mono-Cpmetallocenes is found in EP-A-416,815, WO 95/07942, WO 96/13529, andU.S. Pat. Nos. 5,096,867 and 5,621,126. Specific heteroatom substitutionof the 3- and 2-position of indenyl complexes of group 4 metals wasdisclosed in WO98/06727 and WO/98/06728 respectively.

[0006] Despite the advance in the art, particular higher usetemperature, obtained by such prior art metal complexes as weredisclosed in the foregoing reference, there remains a desire forimproved metal complexes capable of even further increase in usetemperature that are still capable of forming catalyst compositionsuseful in producing polymers having high molecular weights and, forethylene/higher α-olefin copolymers, high incorporation of comonomer.The subject compositions of this invention show unexpected improvementin these desirable features.

SUMMARY OF THE INVENTION

[0007] According to the present invention there are provided metalcomplexes corresponding to the formula:

[0008] where M is a Group 4 metal that is in the +2, +3 or +4 formaloxidation state;

[0009] R^(A) independently each occurrence is hydrogen, or ahydrocarbyl, halohydrocarbyl, hydrocarbyloxyhydrocarbyl,dihydrocarbylaminohydrocarbyl, dihydrocarbylamino, hydrocarbyloxy,hydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl group of from 1 to80 atoms, not counting hydrogen, or further optionally, two or moreR^(A) groups may be covalently linked together;

[0010] Z is (R^(D))₂Si=, wherein R^(D) independently each occurrence isC₇₋₂₀ alkaryl or two R^(D) groups together are alkyl-orpolyalkyl-substituted arylene of up to 40 carbons; and

[0011] Y is bonded to M and Z and is selected from the group consistingof —O—, —S—, —NR^(E)—, and —PR^(E)—; wherein, R^(E) independently eachoccurrence is hydrogen, or a member selected from hydrocarbyl,hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, andcombinations thereof, said R^(E) having up to 20 nonhydrogen atoms

[0012] X is an anionic or dianionic ligand group having up to 60 atomsexclusive of the class of ligands that are cyclic, delocalized, π-boundligand groups;

[0013] X′ independently each occurrence is a neutral ligand having up to40 atoms;

[0014] p is zero, 1 or 2, and is two less than the formal oxidationstate of M when X is an anionic ligand, and when X is a dianionic ligandgroup, p is 1; and

[0015] q is zero, 1 or 2.

[0016] The above complexes may exist as isolated crystals optionally inpure form or as a mixture with other complexes, in the form of asolvated adduct, optionally in a solvent, especially an organic liquid,in the form of a dimer or chelated derivative thereof, wherein thechelating agent is an organic material, preferably a Lewis base,especially a dihydrocarbylether, cyclic aliphatic ether,trihydrocarbylamine, trihydrocarbylphosphine, or halogenated derivativethereof, or as a polymeric or crosslinked polymeric product, wherein oneor more R^(A) groups are polymerized with one another or copolymerizedwith an ethylenically unsaturated comomomer.

[0017] Also, according to the present invention, there is provided acatalyst composition, useful, inter alia, for the polymerization ofaddition polymerizable monomers, comprising the following components orthe reaction product thereof:

[0018] (A) one or more metal complexes of formula (I) or (II); and

[0019] (B) an activating cocatalyst, wherein the molar ratio of (A) to(B) is from 1:10,000 to 100:1.

[0020] Another embodiment of this invention is the foregoing catalystcomposition wherein the metal complex is in the form of a radicalcation.

[0021] Further according to the present invention there is provided apolymerization process comprising contacting one or more additionpolymerizable monomers under polymerization conditions with one of theaforementioned catalyst compositions.

[0022] A preferred process of this invention is a high temperaturesolution polymerization process comprising contacting one or moreaddition polymerizable monomers under polymerization conditions with oneof the aforementioned catalyst systems at a temperature from 50° C. to250° C., preferably from 150° C. to 250° C., most preferably from 175°C. to 220° C. Within the scope of this invention are the polymericproducts produced by the aforementioned processes.

[0023] This invention also includes the precursor of the delocalizedelectron containing, cyclic moiety of the metal complex of formula (I),said precursor corresponding to the formula:

[0024] wherein, Y′ is —OR^(C), —SR^(C), —NR^(C)R^(E), —PR^(C)R^(E);

[0025] R^(C) independently each occurrence is hydrogen, an alkali metalcation, or a magnesium halide cation, or both R^(C) groups together arean alkaline earth metal dication;

[0026] Z* is (R^(D))₂Si═, wherein R^(D) independently each occurrence isC₇₋₂₀ alkaryl or two R^(D) groups together are alkyl- orpolyalkyl-substituted arylene of up to 40 carbons; and

[0027] R^(A) and R^(E) are as previously defined.

[0028] It is to be understood that the foregoing formulas (IA) and (IIA)depict one of several equivalent interannular, double bond isomers, andthat all such isomeric structures are intended to be included by theformulas.

[0029] The final embodiment of the invention is the use of one of theforegoing compounds of formula (IA) or (IIA) in a synthesis to produce aGroup 4 metal complex of formula (I) or (II).

[0030] The present catalysts and processes are especially suited for usein the production of high molecular weight polymers of olefin monomers,over a wide range of polymerization conditions, and especially atelevated temperatures, with exceptionally high catalyst efficiencies.They are especially useful for the solution polymerization of ethylenehomopolymers, copolymers of ethylene with an α-olefin other thanethylene (ethylene/α-olefin copolymers), and ethylene/propylene/dieneinterpolymers (EPDM polymers) wherein the diene is ethylidenenorbornene,1,4-hexadiene or similar nonconjugated diene. The use of elevatedtemperatures dramatically increases the productivity of such processesdue to the fact that increased polymer solubility at elevatedtemperatures allows the use of increased conversions (higherconcentration of polymer product) without exceeding solution viscositylimitations of the polymerization equipment as well as reduced energycosts needed to devolatilize the reaction product. In the preparationparticularly of copolymers of ethylene and at least one α-olefincomonomer, the present catalyst compositions incorporate relativelylarge quantities of non-ethylene comomomer compared to catalystscomprising a conventional metal. In particular, ethylene/1-octenecopolymers having reduced density due to increased incorporation of1-octene therein, may be made using the present catalyst compositions.

[0031] The metal complexes of this invention may also be supported on asupport material and used in olefin polymerization processes in a slurryor in the gas phase. Additionally, those complexes wherein R^(A) isethylenically unsaturated may be used to form polymeric reactionproducts via polymerization of copolymerization of such ethylenicunsaturation in the R^(A) moiety. Such products may be employed in aslurry or gas phase polymerization without need for an additionalsupport material. Such a polymeric catalyst may be formed byprepolymerization of the functionalized metal complex, optionally withone or more ethylenically unsaturated monomers, in situ in apolymerization reactor or in a separate reactor with recovery of theprepolymerized catalyst prior to the primary polymerization process.

BRIEF DESCRIPTION OF THE DRAWINGS

[0032]FIG. 1 shows the single crystal structure derived by X-rayanalysis (ORTEP) of(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7aη)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-[(dimethylsilylene)bis(methylene)]titanium(Example 7).

[0033]FIG. 2 shows the single crystal structure derived by X-rayanalysis (ORTEP) of(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl) (Example 8).

DETAILED DESCRIPTION

[0034] All reference to the Periodic Table of the Elements herein shallrefer to the Periodic Table of the Elements, published and copyrightedby CRC Press, Inc., 1997. Also, any reference to a Group or Groups shallbe to the Group or Groups as reflected in this Periodic Table of theElements using the IUPAC system for numbering groups. As used herein theterm “comprising” is not intended to exclude any additional component,additive or step. For purposes of United States patent practice, thecontents of any patent, patent application or publication referencedherein are hereby incorporated by reference in their entirety,especially with respect to the disclosure of synthetic techniques andgeneral knowledge in the art.

[0035] In a preferred embodiment of the invention, R^(D) is C₁₋₁₀ alkylsubstituted phenyl group, preferably a C₄₋₁₀ alkyl substituted phenylgroup. In addition, it is independently highly desirable that R^(D) issubstituted in the para position or is a mixture of C₁₋₁₀ alkylphenylsubstitution isomers. A most preferred R^(D) group is p-n-butylphenyl.

[0036] Preferred compounds according to the invention are thosecompounds of formula (I) corresponding to the formula:

[0037] where R^(B′) corresponds to the formula N(R^(B))₂, wherein R^(B)each occurrence is C₁₋₁₀ hydrocarbyl, or a halo- or tri(C₁₋₄hydrocarbyl)silyl-substituted derivative thereof, or two R^(B) groupstogether form a divalent hydrocarbon moiety, or a halo- or tri(C₁₋₄hydrocarbyl)silyl-substituted derivative thereof, said divalent groupcontaining from 4 to 40 atoms not counting hydrogen; and

[0038] R^(A), Z, M, X, X′, p and q are as previously defined.

[0039] Most preferably, N(R^(B))₂, is dibenzylamino or two R^(B) groupstogether with the nitrogen atom form a cycloaliphatic group, optionallysubstituted with an aromatic group. In a most preferred embodiment, thecycloaliphatic group is substituted with an aromatic group, which morepreferably still, is a benzannulated ligand, which, together with bothR^(B) groups forms a multiple ring, fused heteroatomic group. Thus, mostpreferably, —N(R^(B))₂ is in the form of a multiple ring, fused,aza-cyclic group. Examples of the foregoing, —N(R^(B))₂ groups include:1,3-dihydro-2H-isoindol-2-yl, 1,2,3,4-tetrahydro-2H-isoquinoline-2-yl,1,3-dihydro-2H-benzo[f]isoindol-2-yl,1,3-dihydro-2H-benzo[e]isoindol-2-yl,1,2,3,4-tetrahydro-2H-benzo[g]isoquinoline-2-yl,1,2,3,4-tetrahydro-2H-benzo[f]isoquinoline-2-yl,1,2,3,4-tetrahydro-2H-benzo[h]isoquinoline-2-yl,1H-benzo[de]isoquinolin-2(3H)-yl, and dibenzylamino groups,corresponding to the following formulas:

[0040] A preferred Group 4 metal for all of the present metal complexesis titanium.

[0041] Preferred X groups are halo, C₁₋₁₀ hydrocarbyl ortrialkylsilylalkyl groups of up to 20 caarbons, or two such X groupstogether form a divalent ligand group. Most preferred X groups arechloro, methyl, trimethylsilylmethyl, or two X groups together are(dimethylsilylene)bis-(methylene), most preferably trimethylsilylmethyl,or two X groups together are (dimethylsilylene)bis(methylene). In theembodiments wherein X is trimethylsilylmethyl the complexes possessimproved catalytic activity. In the embodiments wherein two X groupstogether are (dimethylsilylene)bis(methylene) the metal complexesadditionally are particularly stable (robust) under typical storage anduse conditions.

[0042] Preferred R^(A) groups (other than the —NR^(B) groups previouslydisclosed at the 3 position of compounds of formula (I)) are hydrogen,or an alkyl, aryl or aralkyl group of up to 10 carbons.

[0043] Preferably in all embodiments of the invention, Y is —NR^(E)—where R^(E) is C₁₋₆ alkyl or cycloalkyl, preferably isopropyl,cyclohexyl, or t-butyl.

[0044] Preferred X′ groups in all of the foregoing embodiments of theinvention are carbon monoxide; phosphines, especiallytrimethylphosphine, triethylphosphine, triphenylphosphine andbis(1,2-dimethylphosphino)ethane; P(OR^(K))₃, wherein R^(K),independently each occurrence, is hydrocarbyl, silyl orsilylhydrocarbyl; ethers, especially tetrahydrofuran; amines, especiallypyridine, bipyridine, tetramethylethylenediamine (TMEDA), ortriethylamine; olefins; and conjugated dienes having from 4 to 40 carbonatoms. Complexes including the latter X′ groups, especially terminallyhydrocarbyl substituted-1,3-butadienes, include those wherein the metalis in the +2 formal oxidation state.

[0045] In the foregoing compounds when p is 2, q is zero, M is in the +3or +4 formal oxidation state, and X independently each occurrencepreferably is chloride, methyl, benzyl, trimethylsilylmethyl, allyl,pyrollyl or two X groups together are 1,4-butane-diyl,2-butene-1,4-diyl, 2,3-dimethyl-2-butene-1,4-diyl,2-methyl-2-butene-1,4-diyl, xylyldiyl, or(dimethylsilylene)bis(methylene). Additionally, when p is 1, q is zero,M is in the +3 formal oxidation state, and X is preferably,2-(N,N-dimethyl)aminobenzyl, 2-(N,N-dimethylaminomethyl)phenyl, allyl,or methallyl. Finally, when p is 0, q is 1, M is in the +2 formaloxidation state, and X′ is 1,4-diphenyl-1,3-butadiene, 1,3-pentadiene or2,4-hexadiene.

[0046] Highly preferred complexes according to the invention correspondto the formulas:

[0047] where R^(F) is C₁₋₁₀ alkyl substituted phenyl, preferably C₄-₁₀alkyl substituted phenyl, most preferably n-butylphenyl, most highlypreferably para-n-butylphenyl;

[0048] R^(I) is chloro, methyl, benzyl, trimethylsilylmethyl or twoR^(I) groups together are (dimethylsilylene)bis(methylene); and

[0049] R^(J) is allyl, 2-(dimethylamino)benzyl, 1,4-pentadiene or1,4-diphenyl-1,3-butadiene.

[0050] Illustrative metal complexes according to the present inventioninclude:

[0051]dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium;

[0052](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-,η-cyclopentadienyl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0053](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-,η-cyclopentadienyl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0054](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-,η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0055](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;

[0056](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0057]dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium;

[0058](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0059](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0060](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0061](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;

[0062](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0063]dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;

[0064](N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0065](N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0066](N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0067](N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;

[0068](N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0069]dichloro(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;

[0070](N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0071](N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0072](N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0073](N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III)2-(N,N-dimethylamino)benzyl;

[0074](N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0075]dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;

[0076](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0077](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0078](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0079](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;

[0080](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0081]dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;

[0082](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0083](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0084](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0085](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;

[0086](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0087]dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;

[0088](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0089](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0090](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0091](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;

[0092](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0093]dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;

[0094](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0095](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0096](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0097](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;

[0098](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0099]dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;

[0100](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0101](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0102](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0103](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;

[0104](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0105]dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;

[0106](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0107](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0108](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0109](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;

[0110](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0111]dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;

[0112](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0113](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0114](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0115](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl))-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;

[0116](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0117]dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;

[0118](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0119](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0120](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0121](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;

[0122](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0123]dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;

[0124](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0125](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0126](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0127](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III)2-(N,N-dimethylamino)benzyl;

[0128](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0129]dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;

[0130](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0131](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0132]N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0133](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;

[0134](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0135]dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;

[0136](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0137](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0138](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0139](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;

[0140](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0141]dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;

[0142](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0143](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0144](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0145](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;

[0146](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0147]dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;

[0148](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0149](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0150](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)iphenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0151](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;

[0152](N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-indene-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;

[0153]dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;

[0154](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;

[0155](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);

[0156]N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);

[0157](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl; and

[0158](N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene.

[0159] The complexes can be prepared by use of well known synthetictechniques. The reactions are conducted in a suitable noninterferingsolvent at a temperature from −100 to 300° C., preferably from −78 to100° C., most preferably from 0 to 50° C. Suitable reaction media forthe formation of the complexes include aliphatic and aromatichydrocarbons, ethers, and cyclic ethers, particularly branched-chainhydrocarbons such as isobutane, butane, pentane, hexane, heptane,octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such ascyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, andmixtures thereof; aromatic and hydrocarbyl-substituted aromaticcompounds such as benzene, toluene, and xylene, C₁₋₄ dialkyl ethers,C₁₋₄ dialkyl ether derivatives of (poly)alkylene glycols, andtetrahydrofuran. Mixtures of the foregoing are also suitable.

[0160] Optionally a reducing agent can be employed to produce the loweroxidation state complexes. By the term “reducing agent” herein is meanta metal or compound which, under reducing conditions causes the metal M,to be reduced from a higher to a lower oxidation state. Examples ofsuitable metal reducing agents are alkali metals, alkaline earth metals,aluminum and zinc, alloys of alkali metals or alkaline earth metals suchas sodium/mercury amalgam and sodium/potassium alloy. Examples ofsuitable reducing agent compounds are sodium naphthalenide, potassiumgraphite, lithium alkyls, lithium or potassium alkadienyls; and Grignardreagents. Most preferred reducing agents are the alkali metals oralkaline earth metals, especially lithium and magnesium metal. Suitabletechniques for preparing complexes of the present invention are wellknown to the skilled artisan and may be readily derived from techniquestaught, for example, in the previously mentioned publication, WO98/06727(U.S. Ser. No. 230,185, filed Jul. 28, 1997).

[0161] The complexes are rendered catalytically active by combinationwith an activating cocatalyst or use of an activating technique, such asthose that are previously known in the art for use with Group 4 metalolefin polymerization complexes. Suitable activating cocatalysts for useherein include polymeric or oligomeric alumoxanes, especiallymethylalumoxane, triisobutyl aluminum modified methylalumoxane, orisobutylalumoxane; neutral Lewis acids, such as C₁₋₃₀ hydrocarbylsubstituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- ortri(hydrocarbyl)boron compounds and halogenated (includingperhalogenated) derivatives thereof, having from 1 to 10 carbons in eachhydrocarbyl or halogenated hydrocarbyl group, more especiallyperfluorinated tri(aryl)boron compounds, and most especiallytris(pentafluoro-phenyl)borane; nonpolymeric, compatible,noncoordinating, ion forming compounds (including the use of suchcompounds under oxidizing conditions), especially the use of ammonium-,phosphonium-, oxonium-, carbonium-, silylium- or sulfonium-salts ofcompatible, noncoordinating anions, or ferrocenium salts of compatible,noncoordinating anions; bulk electrolysis (explained in more detailhereinafter); and combinations of the foregoing activating cocatalystsand techniques. The foregoing activating cocatalysts and activatingtechniques have been previously taught with respect to different metalcomplexes in the following references: EP-A-277,003, U.S. Pat. Nos.5,153,157, 5,064,802, 5,321,106, 5,721,185, 5,350,723, 5,425,872,5,625,087, 5,883,204, 5,919,983, 5,783,512, WO 99/15534, and U.S. Ser.No. 09/251,664, filed Feb. 17, 1999.

[0162] Combinations of neutral Lewis acids, especially the combinationof a trialkylaluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to20 carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, further combinations of such neutralLewis acid mixtures with a polymeric or oligomeric alumoxane, andcombinations of a single neutral Lewis acid, especiallytris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxaneare especially desirable activating cocatalysts. Preferred molar ratiosof Group 4 metal complex:tris(pentafluoro-phenylborane:alumoxane arefrom 1:1:1 to 1:10:30, more preferably from 1:1:1.5 to 1:5:10.

[0163] Suitable ion forming compounds useful as cocatalysts in oneembodiment of the present invention comprise a cation which is aBronsted acid capable of donating a proton, and a compatible,noncoordinating anion, A⁻. As used herein, the term “noncoordinating”means an anion or substance which either does not coordinate to theGroup 4 metal containing precursor complex and the catalytic derivativederived therefrom, or which is only weakly coordinated to such complexesthereby remaining sufficiently labile to be displaced by a neutral Lewisbase. A noncoordinating anion specifically refers to an anion which whenfunctioning as a charge balancing anion in a cationic metal complex doesnot transfer an anionic substituent or fragment thereof to said cationthereby forming neutral complexes. “Compatible anions” are anions whichare not degraded to neutrality when the initially formed complexdecomposes and are noninterfering with desired subsequent polymerizationor other uses of the complex.

[0164] Preferred anions are those containing a single coordinationcomplex comprising a charge-bearing metal or metalloid core which anionis capable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitriles. Suitable metals include,but are not limited to, aluminum, gallium, niobium or tantalum. Suitablemetalloids include, but are not limited to, boron, phosphorus, andsilicon. Compounds containing anions which comprise coordinationcomplexes containing a single metal or metalloid atom are, of course,well known and many, particularly such compounds containing a singleboron atom in the anion portion, are available commercially.

[0165] Preferably such cocatalysts may be represented by the followinggeneral formula:

(L*—H)_(d) ⁺(A)^(d−)

[0166] wherein:

[0167] L* is a neutral Lewis base;

[0168] (L*—H)⁺ is a conjugate Bronsted acid of L*;

[0169] A^(d−) is a noncoordinating, compatible anion having a charge ofd−, and

[0170] d is an integer from 1 to 3.

[0171] More preferably A^(d−) corresponds to the formula: [M′Q₄]⁻;

[0172] wherein:

[0173] M′ is boron or aluminum in the +3 formal oxidation state; and

[0174] Q independently each occurrence is selected from hydride,dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halo-substitutedhydrocarbyl, halo-substituted hydrocarbyloxy, and halo-substitutedsilylhydrocarbyl radicals (including perhalogenatedhydrocarbyl-perhalogenated hydrocarbyloxy- and perhalogenatedsilylhydrocarbyl radicals), said Q having up to 20 carbons with theproviso that in not more than one occurrence is Q halide. Examples ofsuitable hydrocarbyloxide Q groups are disclosed in U. S. Pat. No.5,296,433.

[0175] In a more preferred embodiment, d is one, that is, the counterion has a single negative charge and is A⁻. Activating cocatalystscomprising boron which are particularly useful in the preparation ofcatalysts of this invention may be represented by the following generalformula:

(L*—H)⁺(BQ₄)⁻;

[0176] wherein:

[0177] L* is as previously defined;

[0178] B is boron in a formal oxidation state of 3; and

[0179] Q is a hydrocarbyl-, hydrocarbyloxy-, fluorohydrocarbyl-,fluorohydrocarbyloxy-, hydroxyfluorohydrocarbyl-,dihydrocarbylaluminumoxyfluorohydrocarbyl-, or fluorinatedsilylhydrocarbyl-group of up to 20 nonhydrogen atoms, with the provisothat in not more than one occasion is Q hydrocarbyl. Most preferably, Qis each occurrence a fluorinated aryl group, especially, apentafluorophenyl group.

[0180] Preferred Lewis base salts are ammonium salts, more preferablytrialkylammonium salts containing one or more C₁₂-₄₀ alkyl groups.

[0181] Illustrative, but not limiting, examples of boron compounds whichmay be used as an activating cocatalyst in the preparation of theimproved catalysts of this invention are tri-substituted ammonium saltssuch as:

[0182] trimethylammonium tetrakis(pentafluorophenyl)borate,

[0183] triethylammonium tetrakis(pentafluorophenyl)borate,

[0184] tripropylammonium tetrakis(pentafluorophenyl)borate,

[0185] tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,

[0186] tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,

[0187] N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

[0188] N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate,

[0189] N,N-dimethylanilinium benzyltris(pentafluorophenyl)borate,

[0190] N,N-dimethylaniliniumtetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate,

[0191] N,N-dimethylaniliniumtetrakis(4-(triisopropylsilyl)-2,3,5,6.-tetrafluorophenyl)borate,

[0192] N,N-dimethylaniliniumpentafluorophenoxytris(pentafluorophenyl)borate,

[0193] N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,

[0194] N,N-dimethyl-2,4,6-trimethylaniliniumtetrakis(pentafluorophenyl)borate,

[0195] dimethyltetradecylammonium tetrakis(pentafluorophenyl)borate,

[0196] dimethylhexadecylammonium tetrakis(pentafluorophenyl)borate,

[0197] dimethyloctadecylammonium tetrakis(pentafluorophenyl)borate,

[0198] methylditetradecylammonium tetrakis(pentafluorophenyl)borate,

[0199]methylditetradecylammonium(hydroxyphenyl)tris(pentafluorophenyl)borate,

[0200]methylditetradecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl)borate,

[0201] methyldihexadecylammonium tetrakis(pentafluorophenyl)borate,

[0202]methyldihexadecylammonium(hydroxyphenyl)tris(pentafluorophenyl)borate,

[0203]methyldihexadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl)borate,

[0204] methyldioctadecylammonium tetrakis(pentafluorophenyl)borate,

[0205]methyldioctadecylammonium(hydroxyphenyl)tris(pentafluorophenyl)borate,

[0206]methyldioctadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl)borate,mixtures of the foregoing, dialkyl ammonium salts such as:

[0207] di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,

[0208] methyloctadecylammonium tetrakis(pentafluorophenyl)borate,

[0209] methyloctadodecylammonium tetrakis(pentafluorophenyl)borate, and

[0210] dioctadecylammonium tetrakis(pentafluorophenyl)borate;

[0211] tri-substituted phosphonium salts such as:

[0212] triphenylphosphonium tetrakis(pentafluorophenyl)borate,

[0213] methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate,and

[0214] tri(2,6-dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate;

[0215] di-substituted oxonium salts such as:

[0216] diphenyloxonium tetrakis(pentafluorophenyl)borate,

[0217] di(o-tolyl)oxonium tetrakis(pentafluorophenyl)borate, and

[0218] di(octadecyl)oxonium tetrakis(pentafluorophenyl)borate;

[0219] di-substituted sulfonium salts such as:

[0220] di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate, and

[0221] methylcotadecylsulfonium tetrakis(pentafluorophenyl)borate.

[0222] Preferred (L*—H)⁺ cations are methyldioctadecylammonium anddimethyloctadecylammonium. The use of the above Bronsted acid salts asactivating cocatalysts for addition polymerization catalysts is known inthe art, having been disclosed in U.S. Pat. Nso. 5,064,802, 5,919,983,5,783,512 and elsewhere.

[0223] Another suitable ion forming, activating cocatalyst comprises asalt of a cationic oxidizing agent and a noncoordinating, compatibleanion represented by the formula:

(Ox ^(e+))_(d)(A^(d−))_(e).

[0224] wherein:

[0225] Ox^(e+) is a cationic oxidizing agent having a charge of e+;

[0226] e is an integer from 1 to 3; and

[0227] A^(d−) and d are as previously defined.

[0228] Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Preferred embodimentsof A^(d−) are those anions previously defined with respect to theBronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate. The use of the above salts asactivating cocatalysts for addition polymerization catalysts is known inthe art, having been disclosed in U.S. Pat. No. 5,321,106.

[0229] Another suitable ion forming, activating cocatalyst comprises acompound which is a salt of a carbenium ion and a noncoordinating,compatible anion represented by the formula:

Ĉ⁺A⁻

[0230] wherein:

[0231] Ĉ⁺ is a C₁₋₂₀ carbenium ion; and

[0232] A⁻ is as previously defined. A preferred carbenium ion is thetrityl cation, that is triphenylmethylium. The use of the abovecarbenium salts as activating cocatalysts for addition polymerizationcatalysts is known in the art, having been disclosed in U.S. Pat. No.5,350,723.

[0233] A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:

R₃Si(X′)_(q) ⁺A⁻

[0234] wherein:

[0235] R is C₁₋₁₀ hydrocarbyl, and X′, q and A⁻ are as previouslydefined.

[0236] Preferred silylium salt activating cocatalysts aretrimethylsilylium tetrakispentafluorophenylborate, triethylsilyliumtetrakispentafluorophenylborate and ether substituted adducts thereof.The use of the above silylium salts as activating cocatalysts foraddition polymerization catalysts is known in the art, having beendisclosed in U.S. Pat. No. 5,625,087.

[0237] Certain complexes of alcohols, mercaptans, silanols, and oximeswith tris(pentafluorophenyl)borane are also effective catalystactivators and may be used according to the present invention. Suchcocatalysts are disclosed in U.S. Pat. No. 5,296,433.

[0238] Another class of suitable catalyst activators are expandedanionic compounds corresponding to the formula:

(A^(1+a) ¹ )b¹(Z¹J¹j¹)^(−c1)d¹,

[0239] wherein:

[0240] A¹ is a cation of charge +a¹,

[0241] Z¹ is an anion group of from 1 to 50, preferably 1 to 30 atoms,not counting hydrogen atoms, further containing two or more Lewis basesites;

[0242] J¹ independently each occurrence is a Lewis acid coordinated toat least one Lewis base site of Z¹, and optionally two or more such J¹groups may be joined together in a moiety having multiple Lewis acidicfimctionality,

[0243] j¹ is a number from 2 to 12 and

[0244] a¹, b¹, c¹, and d¹ are integers from 1 to 3, with the provisothat a¹×b¹ is equal to c¹×d¹.

[0245] The foregoing cocatalysts (illustrated by those havingimidazolide, substituted imidazolide, imidazolinide, substitutedimidazolinide, benzimidazolide, or substituted benzimidazolide anions)may be depicted schematically as follows:

[0246] wherein:

[0247] A¹⁺ is a monovalent cation as previously defined, and preferablyis a trihydrocarbyl ammonium cation, containing one or two C₁₀₋₄₀ alkylgroups, especially the methylbis(tetradecyl)ammonium- ormethylbis(octadecyl)ammonium-cation,

[0248] R⁸, independently each occurrence, is hydrogen or a halo,hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl,(including mono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atomsnot counting hydrogen, preferably C₁₋₂₀ alkyl, and

[0249] J¹ is tris(pentafluorophenyl)borane ortris(pentafluorophenyl)aluminane.

[0250] Examples of these catalyst activators include thetrihydrocarbylammonium-, especially, methylbis(tetradecyl)ammonium- ormethylbis(octadecyl)ammonium-salts of:

[0251] bis(tris(pentafluorophenyl)borane)imidazolide,

[0252] bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide,bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide,bis(tris(pentafluorophenyl)borane)4,5-bis(undecyl)imidazolide,

[0253]bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide,

[0254] bis(tris(pentafluorophenyl)borane)imidazolinide,

[0255] bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide,bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide,bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide,

[0256]bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolinide,

[0257] bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide,

[0258]bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide,

[0259] bis(tris(pentafluorophenyl)alumane)imidazolide,

[0260] bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide,bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide,bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolide,

[0261]bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide,

[0262] bis(tris(pentafluorophenyl)alumane)imidazolinide,

[0263] bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolinide,bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide,

[0264]bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide,

[0265] bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide,and

[0266]bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.

[0267] A further class of suitable activating cocatalysts includecationic Group 13 salts corresponding to the formula:

[M″Q¹ ₂L′_(r)]⁺(Ar^(f) ₃M′Q²)−

[0268] wherein:

[0269] M″ is aluminum, gallium, or indium;

[0270] M′ is boron or aluminum;

[0271] Q¹ is C₁₋₂₀ hydrocarbyl, optionally substituted with one or moregroups which independently each occurrence are hydrocarbyloxy,hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino,hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, orhydrocarbylsulfido groups having from 1 to 20 atoms other than hydrogen,or, optionally, two or more Q¹ groups may be covalently linked with eachother to form one or more fused rings or ring systems;

[0272] Q² is an alkyl group, optionally substituted with one or morecycloalkyl or aryl groups, said Q² having from 1 to 30 carbons;

[0273] L′ is a monodentate or polydentate Lewis base, preferably L′ isreversibly coordinated to the metal complex such that it may bedisplaced by an olefin monomer, more preferably L′ is a monodentateLewis base;

[0274] 1′ is a number greater than zero indicating the number of Lewisbase moieties, L′, and

[0275] Ar^(f) independently each occurrence is an anionic ligand group;preferably Ar^(f) is selected from the group consisting of halide, C₁₋₂₀halohydrocarbyl, and Q¹ ligand groups, more preferably Ar^(f) is afluorinated hydrocarbyl moiety of from 1 to 30 carbon atoms, mostpreferably Ar^(f) is a fluorinated aromatic hydrocarbyl moiety of from 6to 30 carbon atoms, and most highly preferably Ar^(f) is aperfluorinated aromatic hydrocarbyl moiety of from 6 to 30 carbon atoms.

[0276] Examples of the foregoing Group 13 metal salts are alumiciniumtris(fluoroaryl)borates or gallicinium tris(fluoroaryl)boratescorresponding to the formula: [M″Q¹ ₂L′_(r)]⁺(Ar^(f) ₃BQ²)-, wherein M″is aluminum or gallium; Q¹ is C₁₋₂₀ hydrocarbyl, preferably C₁₋₈ alkyl;Ar^(f) is perfluoroaryl, preferably pentafluorophenyl; and Q² is C₁₋₈alkyl, preferably C₁₋₈ alkyl. More preferably, Q¹ and Q² are identicalC₁₋₈ alkyl groups, most preferably, methyl, ethyl or octyl.

[0277] The foregoing activating cocatalysts may also be used incombination. An especially preferred combination is a mixture of atri(hydrocarbyl)aluminum or tri(hydrocarbyl)borane compound having from1 to 4 carbons in each hydrocarbyl group or an ammonium borate with anoligomeric or polymeric alumoxane compound.

[0278] The molar ratio of catalyst/cocatalyst employed preferably rangesfrom 1 :10,000 to 100:1, more preferably from 1:5000 to 10:1, mostpreferably from 1:1000 to 1:1. Alumoxane, when used by itself as anactivating cocatalyst, is employed in large quantity, generally at least100 times the quantity of metal complex on a molar basis.Tris(pentafluorophenyl)borane, where used as an activating cocatalyst isemployed in a molar ratio to the metal complex of form 0.5:1 to 10:1,more preferably from 1:1 to 6:1 most preferably from 1:1 to 5:1. Theremaining activating cocatalysts are generally employed in approximatelyequimolar quantity with the metal complex.

[0279] The catalysts, whether or not supported in any suitable manner,may be used to polymerize ethylenically unsaturated monomers having from2 to 100,000 carbon atoms either alone or in combination. Preferredaddition polymerizable monomers for use herein include olefins,diolefins and mixtures thereof. Preferred olefins are aliphatic oraromatic compounds containing vinylic unsaturation as well as cycliccompounds containing ethylenic unsaturation. Examples of the latterinclude cyclobutene, cyclopentene, norbornene, and norbornenederivatives that are substituted in the 5- and 6-positions with C₁₋₂₀hydrocarbyl groups. Preferred diolefins are C₄₋₄₀ diolefin compounds,including ethylidene norbornene, 1,4-hexadiene, norbornadiene, and thelike. The catalysts and processes herein are especially suited for usein preparation of ethylene/1-butene, ethylene/1-hexene,ethylene/styrene, ethylene/propylene, ethylene/1-pentene,ethylene/4-methyl-1-pentene and ethylene/1-octene copolymers as well asterpolymers of ethylene, propylene and a nonconjugated diene, such as,for example, EPDM terpolymers.

[0280] Most preferred monomers include the C₂-₂₀ α-olefins, especiallyethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, long chainmacromolecular α-olefins, and mixtures thereof. Other preferred monomersinclude styrene, C₁₋₄ alkyl substituted styrene, ethylidenenorbornene,1,4-hexadiene, 1,7-octadiene, vinylcyclohexane, 4-vinylcyclohexene,divinylbenzene, and mixtures thereof with ethylene. Long chainmacromolecular α-olefins are vinyl terminated polymeric remnants formedin situ during continuous solution polymerization reactions. Undersuitable processing conditions such long chain macromolecular units arereadily polymerized into the polymer product along with ethylene andother short chain olefin monomers to give small quantities of long chainbranching in the resulting polymer.

[0281] Preferred monomers include a combination of ethylene and one ormore comonomers selected from monovinyl aromatic monomers,4-vinylcyclohexene, vinylcyclohexane, norbornadiene,ethylidene-norbornene, C₃₋₁₀ aliphatic α-olefins (especially propylene,isobutylene, 1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene,and 1-octene), and C₄₋₄₀ dienes. Most preferred monomers are mixtures ofethylene and styrene; mixtures of ethylene, propylene and styrene;mixtures of ethylene, styrene and a nonconjugated diene, especiallyethylidenenorbornene or 1,4-hexadiene, and mixtures of ethylene,propylene and a nonconjugated diene, especially ethylidenenorbornene or1,4-hexadiene.

[0282] In general, the polymerization may be accomplished at conditionswell known in the prior art for Ziegler-Natta or Kaminsky-Sinn typepolymerization reactions, that is, temperatures from 0-250° C.,preferably 30 to 200° C. and pressures from atmospheric to 10,000atmospheres. Suspension, solution, slurry, gas phase, solid state powderpolymerization or other process condition may be employed if desired. Asupport, especially silica, alumina, or a polymer (especiallypoly(tetrafluoroethylene) or a polyolefin) may be employed, anddesirably is employed when the catalysts are used in a gas phasepolymerization process. The support is preferably employed in an amountto provide a weight ratio of catalyst (based on metal):support from1:10⁶ to 1:10³, more preferably from 1:10⁶ to 1:10⁴.

[0283] In most polymerization reactions the molar ratio ofcatalyst:polymerizable compounds employed is from 10⁻¹²:1 to 10⁻¹:1,more preferably from 10⁻⁹:1 to 10⁻⁵:1.

[0284] Suitable solvents use for solution polymerization are liquidsthat are substantially inert under process conditions encountered intheir usage. Examples include straight and branched-chain hydrocarbonssuch as isobutane, butane, pentane, hexane, heptane, octane, andmixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; perfluorinated hydrocarbons such as perfluorinated C₄₋₁₀alkanes, and alkyl-substituted aromatic compounds such as benzene,toluene, xylene, and ethylbenzene. Suitable solvents also include liquidolefins which may act as monomers or comonomers.

[0285] The catalysts may be utilized in combination with at least oneadditional homogeneous or heterogeneous polymerization catalyst in thesame reactor or in separate reactors connected in series or in parallelto prepare polymer blends having desirable properties. An example ofsuch a process is disclosed in WO 94/00500.

[0286] The catalysts of the present invention are particularlyadvantageous for the production of ethylene homopolymers andethylene/α-olefin copolymers having high levels of long chain branching.The use of the catalysts of the present invention in continuouspolymerization processes, especially continuous, solution polymerizationprocesses, allows for elevated reactor temperatures which favor theformation of vinyl terminated polymer chains that may be incorporatedinto a growing polymer, thereby giving a long chain branch. The use ofthe present catalyst compositions advantageously allows for theeconomical production of ethylene/α-olefin copolymers havingprocessability similar to high pressure, free radical produced lowdensity polyethylene.

[0287] The present catalyst compositions may be advantageously employedto prepare olefin polymers having improved processing properties bypolymerizing ethylene alone or ethylene/α-olefin mixtures with lowlevels of a “H” branch inducing diene, such as norbomadiene,1,7-octadiene, or 1,9-decadiene. The unique combination of elevatedreactor temperatures, high molecular weight (or low melt indices) athigh reactor temperatures and high comonomer reactivity advantageouslyallows for the economical production of polymers having excellentphysical properties and processability. Preferably such polymerscomprise ethylene, a C₃₋₂₀ α-olefin and a “H”-branching comonomer.Preferably, such polymers are produced in a solution process, mostpreferably a continuous solution process.

[0288] The catalyst composition may be prepared as a homogeneouscatalyst by addition of the requisite components to a solvent or diluentin which polymerization will be conducted. The catalyst composition mayalso be prepared and employed as a heterogeneous catalyst by adsorbing,depositing or chemically attaching the requisite components on aninorganic or organic particulated solid. Examples of such solidsinclude, silica, silica gel, alumina, clays, expanded clays (aerogels),aluminosilicates, trialkylaluminum compounds, and organic or inorganicpolymeric materials, especially polyolefins. In a preferred embodiment,a heterogeneous catalyst is prepared by reacting an inorganic compound,preferably a tri(C₁₋₄ alkyl)aluminum compound, with an activatingcocatalyst, especially an ammonium salt of ahydroxyaryl(trispentafluoro-phenyl)borate, such as an ammonium salt of(4-hydroxy-3,5-ditertiarybutylphenyl)tris-(pentafluorophenyl)borate or(4-hydroxyphenyl)-tris(pentafluorophenyl)borate. This activatingcocatalyst is deposited onto the support by coprecipitating, imbibing,spraying, or similar technique, and thereafter removing any solvent ordiluent. The metal complex is added to the support, also by adsorbing,depositing or chemically attaching the same to the support, eithersubsequently, simultaneously or prior to addition of the activatingcocatalyst.

[0289] When prepared in heterogeneous or supported form, the catalystcomposition is employed in a slurry or gas phase polymerization. As apractical limitation, slurry polymerization takes place in liquiddiluents in which the polymer product is substantially insoluble.Preferably, the diluent for slurry polymerization is one or morehydrocarbons with less than 5 carbon atoms. If desired, saturatedhydrocarbons such as ethane, propane or butane may be used in whole orpart as the diluent. Likewise, the α-olefin monomer or a mixture ofdifferent ac-olefin monomers may be used in whole or part as thediluent. Most preferably, at least a major part of the diluent comprisesthe (α-olefin monomer or monomers to be polymerized. A dispersant,particularly an elastomer, may be dissolved in the diluent utilizingtechniques known in the art, if desired.

[0290] At all times, the individual ingredients as well as the recoveredcatalyst components must be protected from oxygen and moisture.Therefore, the catalyst components and catalysts must be prepared andrecovered in an oxygen and moisture free atmosphere. Preferably,therefore, the reactions are performed in the presence of an dry, inertgas, such as, for example, nitrogen.

[0291] The polymerization may be carried out as a batchwise or acontinuous polymerization process. A continuous process is preferred, inwhich event catalyst, ethylene, comonomer, and optionally solvent, arecontinuously supplied to the reaction zone, and polymer productcontinuously removed therefrom.

[0292] Without limiting in any way the scope of the invention, one meansfor carrying out such a polymerization process is as follows: In astirred-tank reactor, the monomers to be polymerized are introducedcontinuously, together with solvent and an optional chain transferagent. The reactor contains a liquid phase composed substantially ofmonomers, together with any solvent or additional diluent and dissolvedpolymer. If desired, a small amount of a “H”-branch inducing diene suchas norbomadiene, 1,7-octadiene or 1,9-decadiene may also be added.Catalyst and cocatalyst are continuously introduced in the reactorliquid phase. The reactor temperature and pressure may be controlled byadjusting the solvent/monomer ratio, the catalyst addition rate, as wellas by cooling or heating coils, jackets or both. The polymerization rateis controlled by the rate of catalyst addition. The ethylene content ofthe polymer product is determined by the ratio of ethylene to comonomerin the reactor, which is controlled by manipulating the respective feedrates of these components to the reactor. The polymer product molecularweight is controlled, optionally, by controlling other polymerizationvariables such as the temperature, monomer concentration, or by thepreviously mention chain transfer agent, such as a stream of hydrogenintroduced to the reactor, as is well known in the art. The reactoreffluent is contacted with a catalyst kill agent such as water. Thepolymer solution is optionally heated, and the polymer product isrecovered by flashing off gaseous monomers as well as residual solventor diluent at reduced pressure, and, if necessary, conducting furtherdevolatilization in equipment such as a devolatilizing extruder. In acontinuous process the mean residence time of the catalyst and polymerin the reactor generally is from about 5 minutes to 8 hours, andpreferably from 10 minutes to 6 hours.

[0293] Ethylene homopolymers and ethylene/α-olefin copolymers areparticularly suited for preparation according to the invention.Generally such polymers have densities from 0.85 to 0.96 g/ml. Typicallythe molar ratio of α-olefin comonomer to ethylene used in thepolymerization may be varied in order to adjust the density of theresulting polymer. When producing materials with a density range of from0.91 to 0.93 the comonomer to monomer ratio is less than 0.2, preferablyless than 0.05, even more preferably less than 0.02, and may even beless than 0.01. In the above polymerization process hydrogen has beenfound to effectively control the molecular weight of the resultingpolymer. Typically, the molar ratio of hydrogen to monomer is less thanabout 0.5, preferably less than 0.2, more preferably less than 0.05,even more preferably less than 0.02 and may even be less than 0.01.

EXAMPLES

[0294] It is understood that the present invention is operable in theabsence of any component which has not been specifically disclosed. Thefollowing examples are provided in order to further illustrate theinvention and are not to be construed as limiting. Unless stated to thecontrary, all parts and percentages are expressed on a weight basis. Theterm “overnight”, if used, refers to a time of approximately 16-18hours, “room temperature”, if used, refers to a temperature of about20-25° C., and “mixed alkanes” refers to a mixture of hydrogenatedpropylene oligomers, mostly C₆-C₁₂ isoalkanes, available commerciallyunder the trademark Isopar E™ from Exxon Chemicals Inc. HRMS refers tohigh resolution mass spectroscopy.

[0295] All solvents were purified using the technique disclosed byPangborn et al, Organometallics, 15, 1518-1520, (1996). All compounds,solutions, and reactions were handled under an inert atmosphere (drybox). ¹H and ¹³C NMR shifts were referenced to internal solventresonances and are reported relative to TMS.

[0296] X-ray analysis was performed in the following manner:

[0297] Data Collection: A single crystal of suitable dimensions wasimmersed in oil, Paratone N™, available from Exxon Chemicals, Inc., andmounted on a thin glass fiber. The crystal was transferred to a BrukerSMART PLATFORM diffractometer equipped with a graphite monochromaticcrystal, a MoKα radiation source (λ=0.71073 Å), and a CCD (chargecoupled device) area detector. The crystal was bathed in a cold nitrogenstream for the duration of data collection (−100° C.).

[0298] Program SMART (available from Bruker AXS, Inc., Madison, Wis.,USA) was used for diffractometer control, frame scans, indexing,orientation matrix calculations, least squares refinement of cellparameters, crystal faces measurements and the actual data collection.Program ASTRO (available from Bruker AXS, Inc., Madison, Wis., USA) wasused to set up data collection strategy.

[0299] Raw data frames were read by program SAINT (available from BrukerAXS, Inc., Madison, Wis., USA) and integrated using 3D profilingalgorithms. The resulting data were reduced to produce hkl reflectionsand their intensities and estimated standard deviations. The data werecorrected for Lorentz and polarization effects. Sufficient reflectionswere collected to represent a range of 1.51 to 2.16 redundancy levelwith an R_(sym) value range of 2.5 percent, at the lowest 2θ shell ofreflections, to 3.0 percent at the highest 20 shell of reflections(55°). Crystal decay correction was applied and was less than 1 percent.The unit cell parameters were refined by least squares of the settingangles of the reflections.

[0300] Absorption corrections were applied by integration based onindexed measured faces. Data preparation was carried out using programXPREP (available from Bruker AXS, Inc., Madison, Wis., USA). Thestructure was solved by direct methods in SHELXTL5.1 (available fromBruker AXS, Inc., Madison, Wis., USA) from which the positions of all ofthe non-H atoms were obtained. The structure was refined, also inSHELXTL5.1, using full-matrix least-squares refinement. The non-H atomswere refined with anisotropic thermal parameters and all of the H atomswere calculated in idealized positions and refined riding on theirparent atoms, or were obtained from a Difference Fourier map and refinedwithout any constraints. A correction for secondary extinction was notapplied. The final refinement was carried out using F² rather than Fvalues. R₁ is calculated to provide a reference to the conventional Rvalue but its function is not minimized. Additionally, wR₂ is thefunction that is minimized, and not R₁.

[0301] The linear absorption coefficient, atomic scattering factors andanomalous-dispersion corrections were calculated from values from theInternational Tables for X-ray Crystallography (1974). Vol. IV, p. 55.Birmingham: Kynoch Press (Present distributor, D. Reidel, Dordrecht.).

[0302] Relevant functions:

R ₁=Σ(||F _(o) |−|F _(c)||)/Σ|F _(o)|

wR ₂ =[Σ[w(F _(o) ² −F _(c) ²)² ]/Σ[wF _(o) ²²]]^(½)

R _(int.) =Σ|F _(o) ² −F _(o) ²(mean)|² /Σ[F _(o) ²]

S=[Σ[w(F _(o) ² −F _(c) ²)²]/(n−p)]^(½)

[0303] where n is the number of reflections and p is the total number ofparameters refined

w=1/[σ²(F _(o) ²)+(0.0370*p)²+0.31*p],p=[max(F _(o) ²,0)+2*F _(c) ²]/3

Example 1 Preparation ofdichloro(N-(1,1-dimethylethyl)-1,1-di(p-tolyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium

[0304]

[0305] (A) Preparation ofN-(tert-butyl)-N-(1,1-p-tolyl)-1-(3-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amine

[0306] To a 1.70 g (5.35 mmol) ofN-(tert-butyl)-N-(1-chloro-1,1-di(3-p-tolyl)silylamine dissolved in 20mL of THF was added 1.279 g (5.35 mmol) of1-(1H-3-indenyl)-1-(2,3-dihydro-1H-isoindolinyl) lithium salt dissolvedin 20 mL of THF. After the reaction mixture was stirred for 9 h and thensolvent was removed under reduced pressure. The residue was extractedwith 40 mL of hexane and filtered. Solvent was removed under reducedpressure giving 2.806 of product as a gray solid. Yield 101.9 percent.

[0307]¹H (C₆D₆) δ: 1.10 (s, 9H), 2.01 (s, 3H), 2.08 (s, 3H), 4.12 (d,1H, ³J_(H-H)=1.5 Hz), 4.39 (d, 1H, ²J_(H-H)=11.1 Hz), 4.57 (d, 1H,²J_(H-H)=11.7 Hz), 5.55 (d, 1H, ³J_(H-H)=2.1 Hz), 6.9-7.22 (m, 10H),7.56 (d, 1H, ³J_(H-H)=7.8 Hz), 7.62 (d, 1H, ³J_(H-H)=6.9 Hz), 7.67 (d,1H, ³J_(H-H)=7.8 Hz), 7.83 (d, 1H, ³J_(H-H)=7.8 Hz).

[0308]¹³C{¹H} (C₆D₆) δ: 21.37, 21.43, 33.78, 41.09, 50.05, 56.56,104.28, 120.98, 122.46, 123.84, 124.71, 124.84, 126.98, 128.29, 128.52,129.05, 132.99, 133.68, 135.08, 135.90, 136.01, 138.89, 139.05, 139.09,141.27, 146.39, 148.48.

[0309] (B) Preparation ofN-(tert-butyl)-N-(1,1-p-tolyl)-1-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amine,dilithium salt

[0310] To a 50 mL hexane solution containing 2.726 g (5.61 mmol) of theN-(tert-butyl)-N-(1,1-p-tolyl)-1-(3-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)aminewas added 7.4 mL of 1.6 M n-BuLi solution. During addition of then-BuLi, a yellow precipitate appeared. After stirring for 6 h, theyellow precipitate was collected on a frit, washed with 2×25 mL ofhexane, and dried under reduced pressure to give 2.262 g of the productas a yellow powder. Yield was 76.6 percent.

[0311]¹H (C₆D₆) δ: 1.17 (s, 9H), 2.30 (s, 6H), 4.51 (s, 4H), 6.21 (s,1H), 6.47 (m, 2H), 6.97 (d, 4H, ³J_(H-H)=8.1 Hz), 7.15 (m, 2H), 7.23 (m,2H), 7.50 (m, 1H), 7.81 (d, 4H, ³J_(H-H)=7.8 Hz), 8.07 (d, 1H,³J_(H-H)=7.2 Hz). ¹³C{¹H} (C₆D₆) δ: 21.65, 38.83, 52.46, 59.82, 95.33,112.93, 114.15, 115.78, 118.29, 122.05, 122.60, 124.16, 124.78, 126.94,127.30, 133.06, 134.75, 137.30, 141.98, 148.17.

[0312] (C) Preparation ofdichloro(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium

[0313] In the drybox 1.552 g (4.19 mmol) of TiCl₃(THF)₃ was suspended in20 mL of THF. To this solution, 2.206 g (4.19 mmol) ofN-(tert-butyl)-N-(1,1-p-tolyl)-1-(1,3-dihydro-2H-isoindol-2H-isoindol-2-yl)-1H-indenyl)silyl)amine,dilithium salt dissolved in 30 mL of THF was added within 1 min. Thesolution was then stirred for 60 min. After this time, 0.76 g of PbCl₂(2.75 mmol) was added and the solution was stirred for 60 min. The THFwas then removed under reduced pressure. The residue was first extractedwith 60 mL of methylene chloride and filtered. Solvent was removed underreduced pressure leaving a black crystalline solid. Hexane was added (30mL) and the black suspension was stirred for 10 hour. The solids werecollected on a frit, washed with 30 mL of hexane and dried under reducedpressure to give 2.23 g of the desired product as a deep purple solid.Yield was 88.2 percent.

[0314]¹H (TBF-d₈) δ: 1.40 (s, 9H), 2.46 (s, 3H), 2.48 (s, 3H), 5.07 (d,2H, ²J_(H-H)=12.3 Hz), 5.45 (d, 2H, ²J_(H-H)=12.6 Hz), 5.93 (s, 1H),6.95 (d, 1H, ³J_(H-H)=9.0 Hz), 7.08 (d, 1H, ³J_(H-H)=7.8 Hz), 7.15-7.4(m, 9H), 7.76 (d, 1H, ³J_(H-H)=7.8 Hz), 7.82 (d, 1H, ³J_(H-H)=7.5 Hz),8.05 (d, 1H, ³J_(H-H)=8.7 Hz). ¹³C{¹H} (THF-d₈) δ: 21.71, 21.76, 33.38,56.87, 61.41, 94.5, 107.95, 122.86, 125.77, 126.68, 127.84, 127.92,128.40, 128.49, 129.36, 129.79, 131.23, 131.29, 135.79, 136.43, 136.73,141.02, 141.22, 150.14.

Example 2 Preparationof(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium

[0315]

[0316] In the drybox 0.50 g ofdichloro(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titaniumcomplex (0.79 mmol) was dissolved in 30 mL of diethyl ether. To thissolution, 1.14 mL (1.6 mmol) of MeLi (1.6 M in ether) was added dropwisewhile stirring over a 1 minute period. After the addition of MeLi wascompleted, the solution was stirred for 1.5 hour. Diethyl ether wasremoved under reduced pressure and the residue extracted with 45 mL ofhexane. Hexane was removed under reduced pressure giving a redcrystalline material. This solid was dissolved in about 7 mL of tolueneand 25 mL of hexane, filtered, and the solution was put into the freezer(−27° C.) for 2 days. The solvent was then decanted and the resultingcrystals were washed with cold hexane and dried under reduced pressureto give 156 mg of product. Yield was 33.3 percent

[0317]¹H (C₆D₆) δ: 0.25 (s, 3H), 0.99 (3H), 1.72 (s, 9H), 2.12 (s, 3H),2.15 (s, 3H), 4.53 (d, 2H, ²J_(H-H)=11.7 Hz), 4.83 (d, 2H, ²J_(H-H)=11.7Hz), 5.68 (s, 1H), 6.72 (dd, 1H, ³J_(H-H)=8.6 Hz, ³J_(H-H)=6.6 Hz),6.9-7.2 (m, 11H), 7.30 (d, 1H, ³J_(H-H)=8.6 Hz).7.71 (d, 1H,³J_(H-H)=8.5 Hz), 7.93 (d, 1H, ³J_(H-H)=7.8 Hz), 8.11 (d, 1H,³J_(H-H)=7.8 Hz). ¹³C{¹H} (C₆D₆) δ: 21.45, 21.52, 35.30, 50.83, 56.03,56.66, 57.65, 83.80, 105.64, 122.69, 124.51, 124.56, 125.06, 125.35,127.33, 128.98, 129.06, 129.22, 133.51, 134.02, 134.62, 136.49, 136.84,137.69, 139.72, 139.87, 143.84.

Example 3 Preparation ofdichloro(N-1,1-dimethylethyl)-1,1-(4-butyl-phenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium

[0318]

[0319] A) Tetramethylsilane[MgCl]₂(THF)₆

[0320] To 40 mL diethyl ether solution of 2.5 g, 15.9 mmol ofMe₂Si(CH₂Cl)₂ was added 0.851 g, 35.0 mmol of Mg turnings. Afterstirring overnight, a large amount of white solid was visible. Solventwas removed under reduced pressure and replaced with 40 mL oftetrahydrofuran (THF). Upon addition of THF, all of the white soliddissolved. After stirring an additional 24 h., about 20 mL of hexane wasadded and the solution was filtered. The filtrate was put into a freezer(−27° C.) overnight. Solvent was decanted and large colorless crystalswere washed with cold hexane (2×20 mL). The solid was then dried underreduced pressure to give 2.753 g of product as the THF hexa-adduct.Yield was 27.1 percent

[0321]¹H NMR (THF-d₈): δ−1.81 (s, 4H), −0.21 (s, 6H), 1.77 (m, 28H,THF), 3.66 (m, 28H, THF) ¹³C{¹H} NMR (THF-d₈): δ−2.50, 9.14, 26.37(THF), 68.46 (THF).

[0322] B)dichloro(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-l-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium

[0323] i) Preparation of p-Bu-Ph)₂SiCl₂.

[0324] To a three-necked 250 mL round-bottom flask under a nitrogenatmosphere equipped with a reflux condenser and a 250 mL dropping funnel4.87g of Mg turnings (0.200 moles) were introduced. 1-bromo4-butylbenzene (42.6 g, 0.200 moles) and 80 mL of THF were then added to thedropping funnel. At this time 10 mL of the bromobenzene/THF solution wasadded to the Mg turnings with a small amount of ethyl bromide. Thesolution was then stirred until initiation occurred. The rest of thebromo benzene/THF solution was then added dropwise to allow refluxing tooccur. After addition of the bromo benzene/THF solution, the mixture washeated at reflux until the magnesium was consumed.

[0325] The resulting Grignard solution was then transferred to a 250 mLdropping funnel which was attached to a three-necked 250 mL round-bottomflask under a nitrogen atmosphere equipped with a reflux condenser. Tothe round bottomed flask, 100 mL of heptane was introduced followed bySiCl₄ (15.3 g, 0.090 moles). To this solution, the Grignard solution wasadded dropwise. After addition was complete the resulting mixture wasrefluxed for 2h and then allowed to cool to room temperature. Under aninert atmosphere the solution was filtered. The remaining salts werefurther washed with heptane (3×40 mL), filtered and combined with theoriginal heptane solution.

[0326] The heptane was then removed via distillation at atmosphericpressure. The resulting viscous oil was then vacuum distilled withcollection of the product at 1 mm Hg, (133 Pa) at 210° C. giving 19.3 g(58 percent) of the desired product.

[0327] ii) Preparation of bis(4-n-butylphenyl)(t-butylamido)chlorosilane

[0328] Dichloro-di(4-n-butylphenyl)silane (4.572 g, 12.51 mmol) wasdissolved in 45 mL of methylene chloride. To this solution was added1.83 g, 25.03 mmol of t-BuNH₂. After stirring overnight, the solvent wasremoved under reduced pressure. The residue was extracted with 45 mL ofhexane and filtered. Solvent was removed under reduced pressure leaving4.852 g of the desired product.

[0329] iii) Preparation of(4-n-Bu-Ph)₂Si(3-isoindolino-indenyl)(NH-t-Bu)

[0330] To a 4.612 g (11.47 mmol) of (4-n-Bu-Ph)₂Si(Cl)(NH-t-Bu)dissolved in 20 mL of THF was added 2.744 g (8.37 mmol) of lithium1-isoindolino-indenide dissolved in 30 mL of THF. After the reactionmixture was stir-red overnight solvent was removed under reducedpressure. The residue was extracted with 50 mL of hexane and filtered.Solvent removal gave 6.870 g of product as avery viscous red-brown oil.Yield was 91.0 percent.

[0331] iv) Preparation of dmhthium salt of(4-n-Bu-Ph)₂Si(3-isoindolino-indenyl)(NH-t-Bu)

[0332] To a 50 mL of hexane solution containing 6.186 g (10.33 mmol) of(4-n-Bu-Ph)₂Si(3-isoindolino-indenyl)(NH-t-Bu) was added 13.5 mL of 1.6M n-BuLi solution. A few minutes after n-BuLi addition, a yellowprecipitate appeared. After stirring overnight, the yellow precipitatewas collected on the frit, washed with 4×20 mL of hexane and dried underreduced pressure to give 4.42 g of the desired product as a yellowpowder. Yield was 70.0 percent.

[0333] v) Preparation ofdichloro(N-1,1-dimethylethyl)-1,1-(4-butyl-phenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)sianaminato-(2-)-N-)titanium

[0334] In the drybox, 2.62 g (7.10 mmol) of TiCl₃(THF)₃ was suspended in40 mL of TBF. To this solution, 4.32 g (7.07 mmol) of dilithium salt of(4-n-Bu-Ph)₂Si(3-isoindolino-indenyl)(NH-t-Bu) dissolved in 60 mL of THFwas added within 2 minutes. The solution was then stirred for 60minutes. After this time, 1.28 g of PbCl₂ (4.60 mmol) was added and thesolution was stirred for 60 minutes. The THF was then removed underreduced pressure. The residue was extracted with 50 mL of toluene andfiltered. Solvent was removed under reduced pressure leaving a blackcrystalline solid. Hexane was added (35 mL) and the black suspension wasstirred for 0.5 hour. The solids were collected on the frit, washed with2×30 mL of hexane and dried under reduced pressure to give 4.68 g of thedesired product as a black-blue, crystalline solid. Yield was 92.4percent.

Example 4 Preparation of(N-1,1-dimethylethyl)-1,1-(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-dimethyltitanium

[0335]

[0336]Dichloro(N-1,1-dimethylethyl)-1,1-(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium(1.61 g, 2.25 mmol, Example 14) was suspended in 35 mL of toluene. Tothis suspension was added 3 mL (4.75 mmol) of 1.6 M MeLi ether solution.The reaction color changed at once from dark green-black to dark red.After stirring for 1 hour, the solvent was removed under reducedpressure. The residue was extracted with 55 mL of hexane and filtered.Solvent was removed leaving 1.46 g of the desired product as a redsolid.

Example 5 Preparation of(N-1,1-dimethylethyl)-1,1-(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,3-pentadiene

[0337]

[0338]Dichloro(N-1,1-dimethylethyl)-1,1-(4-butyl-phenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium(1.266 g, 1.77 mmol, Example 14) was suspended in 60 mL of hexane. Themixture was brought to gentle reflux and then 0.9 mL (0.89 mmol) ofpiperylene was added followed by 1.86 mL (3.72 mmol) of BrMgBu (2 M inTHF). The reaction mixture was refluxed for 2.5 hour. After cooling toroom temperature the solution was filtered and solvent was removed underreduced pressure leaving 1.30 g of the desired product as a black glassysolid.

Example 6 Preparation of(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-[(dimethylsilylene)bis(methylene)]titanium

[0339]

[0340] To a 50 mL toluene solution containing 2.33 g, (3.26 mmol) ofdichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl-phenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium(Example 14) was added 3.62 g, 4.23 mmol of Me₂Si(CH₂MgCl)₂(THF)₉ as asolid. After stirring overnight at room temperature, the solution colorchanged from green-black to red. Solvent was removed under reducedpressure. The residue was extracted with 40 mL of hexane and filtered.The solvent was removed under reduced pressure to give a red glassysolid. This material was dissolved in 40 mL of hexane and filteredthought a fine frit. Solvent removal gave 2.16 g of product as a redglassy solid. Yield was 89.0 percent.

[0341]¹H NMR (C₆D₆): δ−0.03 (s, 3H), 0.44 (s, 3H), 0.62 (d, 1H,²J_(H-H)=12.6 Hz), 0/83 (q, 6H, ³J_(H-H)=7.9 Hz), 1.24 (m, 4H), 1.52 (m,4H), 1.54 (s, 9H), 2.34 (s, 2H), 2.45 (d, 1H, ²J_(H-H)=13.4 Hz), 2.52(t, 4H, ³J_(H-H)=7.8 Hz), 4.61 (m, 4H), 5.84 (s, 1H), 6.74 (t, 1H,³J_(H-H)=7.7 Hz), 6.89 (d, 1H, ³J_(H-H)=8.7 Hz), 6.94 (m, 2H), 7.05 (m,2H), 7.15 (d, 2H, ³J_(H-H)=7.5 Hz), 7.26 (d, 2H, ³J_(H-H)=7.8 Hz), 7.31(d, 1H, ³J_(H-H)=9.0 Hz), 7.57 (d, 1H, ³J_(H-H)=8.7 Hz), 8.13 (d, 2H,³J_(H-H)=7.8 Hz), 8.17 (d, 2H, ³J_(H-H)=7.8 Hz).

[0342]¹³C{¹H} NMR (C₆D₆): δ−1.08, −0.28, 14.11, 14.15, 33.70, 33.78,35.91, 36.06, 56.63, 56.88, 80.31, 84.35, 85.24, 103.81, 122.61, 122.81,122.82, 124.27, 124.36, 127.34, 128.47, 128.51, 129.72, 131.03, 134.87,135.00, 136.66, 137.16, 137.79, 143.36, 144.66, 144.85.

[0343] HRMS (El): calculated for C₃₉H₄₆N₂Si₂Ti (M)⁺ 646.2679, found646.2640.

[0344] Analysis: Calculated for C₃₉H₄₆N₂Si₂Ti: C, 72.42; H, 7.17; N,4.33. Found: C, 72.78; H, 7.53; N, 4.13.

Example 7 Preparation of(N-1,1-dimethylethyl)-1,1-(4-methylphenyl)-1--((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-bis[(trinethylsilyl)methyl]-titanium.

[0345]

[0346] In the drybox 3.42 g ofdichloro(N-1,1-dimethylethyl)-1,1-(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium(5.42 mmol) (prepared substantially according to example 5) was partlydissolved in 70 mL of toluene. To this solution 11.6 mL (11.6 mmol) ofLiCH₂TMS (1 M in pentane) was added dropwise while stirring over a oneminute period. After the addition of lithium reagent was completed, thesolution was stirred for 15 hours at room temperature. The reactionmixture was filtered and solvent was removed under reduced pressure. Theresulting solid was dissolved in 15 mL of toluene followed by additionof 45 mL of hexane. The solution was filtered and solvent removed underreduced pressure leaving a red-brown crystalline solid. Hexane was added(25 mL) and the mixture was stirred for 10 min. and then put intofreezer for 24 hours. Red crystalline solid was collected by filtration,washed with 2×8 mL of cold hexane, and then dried under reduced pressureto give 2.722 g of the desired product.

[0347]¹H NMR (C₆D₆): δ−0.67 (d, 2H, ²J_(H-H)=11.7 Hz, —CH₂Si(CH₃)₃),0.14 (s, 9H, —CH₂Si(CH₃)₃), 0.20 (s, 9H, —CH₂Si(CH₃)₃), 1.10 (d, 2H,²J_(H-H)=12.0 Hz, —CH₂Si(CH₃)₃), 1.31 (m, 2H, —CH₂Si(CH₃)₃), 1.71 (s,9H, C(CH₃)₃), 2.13 (s, 6H), 4.77 (d, 2H, ²J_(H-H)=12.0 Hz), 4.91 (d, 2H,²J_(H-H)=12.0 Hz), 5.78 (s, 1H), 6.73 (t, 1H, ³J_(H-H)=7.7 Hz), 6.98 (m,3H), 7.05 (m, 2H), 7.13 (d, 2H, ³J_(H-H)=7.8 Hz), 7.20 (d, 2H,³J_(H-H)=7.8 Hz), 7.33 (d, 1H, ³J_(H-H)=8.4 Hz), 7.78 (d, 1H,³J_(H-H)=9.0 Hz), 7.98 (d, 2H, ³J_(H-H)=7.5 Hz), 8.06 (d, 2H,³J_(H-H)=7.8 Hz).

[0348]¹³C{¹H} NMR (C₆D₆): δ2.74, 3.52, 21.47, 21.50, 35.33, 57.03,58.74, 69.08, 80.50, 84.92, 102.34, 122.57, 124.42, 124.78, 124.92,125.12, 127.55, 128.92, 129.09, 129.49, 133.99, 134.30, 134.60, 136.65,137.09, 137.43, 139.72, 139.83, 146.11.

[0349] HRMS (EI): calculated for C₄₃H₅₈N₂Si₃Ti (M)⁺ 735.3465, found735.3461.

[0350] Analysis Calculated for C₄₃H₅₈N₂Si₃Ti: C, 70.26; H, 7.95; N,3.81. Found: C, 65.96; H, 8.74; N, 2.11.

[0351] The X-ray structure (ORTEP) for the compound is provided in FIG.1.

Example 8 Preparation of(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-[(dimethylsilylene)bis(methylene)]titanium

[0352]

[0353] A) Tetramethylsilane[MgCl]₂(TBF)₆

[0354] To 40 mL diethyl ether solution of 2.5 g, 15.9 mmol ofMe₂Si(CH₂Cl)₂ was added 0.851 g, 35.0 mmol of Mg turnings. Afterstirring overnight large amount of white solid was visible. Solvent wasremoved under reduced pressure and replaced with 40 mL oftetrahydrofuran (THF). Upon addition of THF all of the white soliddissolved. After stirring an additional 24 hr, about 20 mL of hexane wasadded and the solution was filtered. The filtrate was put into a freezer(−27° C.) overnight. Solvent was decanted and large colorless crystalswere washed with cold hexane (2×20 mL). The solid was then dried underreduced pressure to give 2.753 g of product as the THF hexa-adduct.Yield was 27.1 percent.

[0355]¹H NMR (THF-d₈): δ−1.81 (s, 4H), −0.21 (s, 6H), 1.77 (m, 28H,THF), 3.66 (m, 28H, THF).

[0356]¹³C{¹H} NMR (THF-d₈): δ−2.50, 9.14, 26.37 (THF), 68.46 (THF).

[0357] B) Preparation of(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-[(dimethylsilylene)bis-(methylene)]titanium

[0358] To a 50 mL toluene solution containing 0.60 g, 0.95 mmol ofdichloro(N-(1,1-dimethylethyl)-1,1-di(4-methyl-phenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium(prepared substantially according to the technique of Example 5) wasadded 0.667 g, 1.05 mmol of Me₂Si(CH₂MgCl)₂(THF)₆ as a solid. Afterstirring for 2 hours at room temperature, proton NMR analysis showedabout 70 percent conversion to the product. After stirring an additional2 days, the ¹H NMR spectrum did not change. An additional 0.25 g of thediGrigniard was added. Within minutes the reaction mixture turned fromgreen-yellow to red. After stirring an additional 6 hours, the solventwas removed under reduced pressure. The residue was extracted with 40 mLof hexane and filtered. Solvent was removed under reduced pressure togive a red glassy solid. This solid was dissolved back in 15 mL ofhexane. After standing at room temperature overnight, the solvent wasdecanted and red crystals were washed with cold hexane (2×2 mL). Thesecrystals were dried under reduced pressure to give 0.448 g of thedesired product. Yield was 72.9 percent.

[0359]¹H NMR (C₆D₆): δ−0.04 (s, 3H), 0.44 (s, 3H), 0.63 (d, 1H,²J_(H-H)=12.9 Hz), 1.52 (s, 9H), 2.15 (s, 6H), 2.34 (m, 2H), 2.45 (d,1H, ²J_(H-H)=12.9 Hz), 4.61 (m, 4H), 5.81 (s, 1H), 6.74 (t, 1H,³J_(H-H)=7.8 Hz), 6.88 (d, 1H, ³J_(H-H)=6.6 Hz), 6.92 (m, 2H), 7.05 (m,2H), 7.15 (d, 2H, ³J_(H-H)=8.1 Hz), 7.21 (d, 2H, ³J_(H-H)=8.1 Hz), 7.37(d, 1H, ³J_(H-H)=8.4 Hz), 7.56 (d, 1H, ³J_(H-H)=8.4 Hz), 8.09 (d, 2H,³J_(H-H)=6.9 Hz), 8.11 (d, 2H, ³J_(H-H)=7.2 Hz).

[0360]¹³C{¹H} NMR (C₆D₆): δ−1.10, −0.30, 21.50, 21.56, 35.87, 56.62,56.88, 80.27, 84.40, 85.15, 103.75, 122.61, 122.81, 123.83, 124.29,124.37, 127.35, 129.12, 129.68, 130.98, 134.58, 134.61, 136.65, 137.14,137.78, 139.66, 139.86, 143.33.

[0361] HRMS (EI): calculated for C₃₉H₄₆N₂Si₂Ti (M)⁺ 646.2679, found646.2640.

[0362] Analysis: Calculated for C₃₉H₄₆N₂Si₂Ti: C, 72.42; H, 7.17; N,4.33. Found: C, 72.78; H, 7.53; N, 4.13.

[0363] The X-ray structure (ORTEP) for the compound is provided in FIG.2.

Example 9 Preparation ofdichloro(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium

[0364]

[0365] (A) Preparation ofN-(tert-butyl)-N-(1-chloro-1,1-di-p-tolylsilyl)amine

[0366] To a solution of of 10.0 g (35.6 mmol) ofdichloro-p-ditolylsilane in 300 mL of hexane was added 5.20 g (71.1mmol) of t-butyl amine. The reaction mixture was stirred overnight, thenfiltered. The hexane was removed under reduced pressure to give theproduct as a viscous, colorless oil. The yield was 10.83 g (96 percent).

[0367]¹H (C₆D₆) δ: 1.12 (s, 91), 2.04 (s, 6H), 7.01 (d, 4H), 7.82 (d,2H). ¹³C{¹H}(C₆D₆) δ: 21.4, 33.2, 50.80, 129.06, 132.67, 135.09, 140.46.

[0368] (B) Preparation ofN-(tert-butyl)-N-(1,1-di(4-methylphenyl)-1-(3-tetrahydro-1H-1-pyrrolyl-1H-1-indenyl)silyl)amine.A solution of 1-(1H-3-indenyl)pyrrolidine, lithium salt (1.00 g, 5.23mmol) in 40 mL of THF was added dropwise to a 80 mL THF solutionN-(tert-butyl)-N-(1-chloro-1,1-di-p-tolylsilyl)amine (1.66 g, 5.23mmol). After the addition was complete the reaction mixture was stirredovernight. The solvent was then removed under reduced pressure. Theresidue was extracted with hexane and the solution filtered. The solventwas then removed under reduced pressure leaving 2.41 g of product. Yieldwas 99 percent.

[0369]¹H (C₆D₆) δ1.07 (s, 9H), 1.52 (bs, 4H), 2.04 (s, 3H), 2.09 (s,3H), 3.00 (bs, 2H), 3.14 (bs, 2H), 4.07 (s, 1H), 5.52 (s, 1H), 7.00-7.84(m, 12H).

[0370] (C) Preparation ofN-(tert-butyl)-N-(1,1-di(4-methylphenyl)-1-(3-tetrahydro-1H-1-pyrrolyl-1H-1-indenyl)silyl)amine,dilithium salt. In the drybox, 2.41 g (5.16 mmol) ofN-(tert-butyl)-N-(1,1-di(4-methylphenyl)-1-1-(3-tetrahydro-1H-1-pyrrolyl-1H-1-indenyl)silyl)aminewas combined with 80 mL of hexane. To this solution, 6.45 mL (10.33mmol) of n-BuLi (1.6 M in hexanes) was added dropwise. Upon completeaddition of the n-BuLi, the solution was stirred overnight. Theresulting precipitate was collected via filtration, washed with hexaneand dried under reduced pressure to give 1.52 g of product. Yield was 61percent.

[0371] (D) Preparation ofdichloro(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium

[0372]N-(tert-butyl)-N-(1,1-di(4-methylphenyl)-1-(3-tetrahydro-1H-1-pyrrolyl-1H-1-indenyl)silyl)amine,dilithium salt (1.52 g, 3.26 mmol) was added as a solid to a 80 mLsolution of THF containing TiCl₃(THF)₃ (1.21 g 3.26 mmol). After 45 min,PbCl₂ (0.45 g, 1.63 mmol) was added as a solid. The reaction mixture wasthen stirred an additional hour. The solvent was removed under reducedpressure. The residue was extracted with toluene and filtered. Toluenewas removed under reduced pressure and the residue was triturated withhexane. The solid was collected by filtration, washed with hexane andthen dried under reduced pressure. 1.40 g of product was obtained. Yieldwas 73 percent.

[0373]¹H (CDCl₃) δ1.33 (s, 9H), 1.99 (br s, 4H), 2.36 (s, 3H), 2.39 (s3H), 3.65 (br s, 2H), 3.87 (br s, 2H), 5.74 (s, 1H), 7.10 (m, 1H), 7.25(bs, 5H), 7.60 (m, 2H), 7.77 (s, 2H) 7.82 (d, 1H).

[0374]¹³C{¹H}(CDCl₃) 6: 21.01, 21.68, 25.73, 333.35, 50.70, 60.86,83.69, 107.91, 125.58, 126.81, 127.23, 127.98, 128.95, 128.99, 129.37,131.23, 135.48, 136.08, 136.36, 140.33, 140.53, 150.38.

Example 10 Preparation of(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium

[0375]

[0376] In the drybox 0.444 gdichloro(N-(1,1-dimethylethyl)-1,1I-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)titaniumcomplex (0.76 mmol) was dissolved in 30 mL of diethylether. To thissolution 1.00 mL (1.6 mmol) of MeLi (1.6 M in ether) was added dropwisewhile stirring over a 2 minute period. After the addition of MeLi wascompleted, the solution was stirred for 1.5 hour. Et₂O was removed underreduced pressure and the residue extracted with 45 mL of hexane. Hexanewas removed under reduced pressure giving 0.348 mg of red, crystallinematerial. This red solid was dissolved in about 5 mL of hexane (heatingwas used) and then the vial was put into freezer overnight at −27° C.,giving 75 mg of red crystals.

[0377]¹H (C₆D₆) δ: 0.26 (s, 3H), 1.01 (s, 3H), 1.44 (m, 4H), 1.72 (s,9H), 2.01 (s, 3H), 2.14 (s, 3H), 3.12 (m, 2H), 3.36 (m, 2H), 5.60 (s,1H), 6.70 (ddd, 1H, ³J_(H-H)=8.7 Hz, ³J_(H-H)=6.6 Hz, ⁴J_(H-H)=0.9 Hz),6.96 (ddd, 1H, ³J_(H-H)=8.6 Hz, ³J_(H-H)=6.6 Hz, ⁴J_(H-H)=0.9 Hz), 7.12(m, 4H), 7.68 (d, 1H, ³J_(H-H)=8.7 Hz), 7.68 (d, 1H, ³J_(H-H)=9.0 Hz),7.89 (d, 2H, ³J_(H-H)=7.8 Hz), 8.11 (d, 2H, ³J_(H-H)=7.8 Hz).

[0378]¹³C{¹H} (C₆D₆) δ: 21.43, 21.50, 25.82, 35.31, 49.87, 50.45, 55.53,57.45, 83.28, 105.28, 124.31, 124.86, 125.00, 125.50, 128.86, 128.96,129.20, 133.65, 134.08, 134.77, 136.46, 136.81, 139.57, 139.76, 144.86.

[0379] Ethylene/1-Octene Polymerization Conditions

[0380] All liquid and gas feeds were passed through columns of aluminaand a decontaminant (Q-5™ catalyst available from Englehardt ChemicalsInc.) prior to introduction into the reactor. Catalyst components arehandled in a glovebox containing an atmosphere of argon or nitrogen. Astirred 2.0 liter reactor is charged with about 740 g of mixed alkanessolvent and 118 g of 1-octene comonomer. Hydrogen (25 psi, 170 kPa) isadded as a molecular weight control agent by differential pressureexpansion from a 75 mL addition tank. The reactor is heated to 140° C.and saturated with ethylene at 500 psig (3.4 MPa). Metal complex asdilute toluene solution and cocatalyst as dilute solutions in toluene ormethylcyclohexane, were mixed in a 1:1 molar ratio and transferred to acatalyst addition tank and injected into the reactor. The cocatalyst wasmethyldi(octadecyl)ammonium tetrakis(pentafluoro-phenyl)borate, theammonium cation of which is derived from a mixture of amines availablecommercially as methyl bis(tallow)amine. The polymerization conditionswere maintained for 15 minutes with ethylene added on demand. Theresulting solution was removed from the reactor, quenched with isopropylalcohol, and stabilized by addition of a toluene solution containingabout 67 mg/100 g polymer of a hindered phenol antioxidant (Irganox™1010 from Ciba Geigy Corporation) and about 133 mg/100 g polymer of aphosphorus stabilizer (Irgafos 168 from Ciba Geigy Corporation).

[0381] Between sequential polymerization runs, a wash cycle wasconducted in which 850 g of mixed alkanes was added to the reactor andthe reactor was heated to 150° C. The reactor was then emptied of theheated solvent immediately before beginning a new polymerization run.

[0382] Polymers were recovered by drying in a vacuum oven set at 140° C.for about 20 hours. Density values are derived by determining thepolymer's mass when in air and when immersed in methylethyl ketone.Micro melt index values (MMI) are obtained using a Custom ScientificInstrument Inc. Model CS-127MF-015 apparatus at 190° C., and are unitless values calculated as follows: MMI=1/(0.00343 t−0.00251), wheret=time in seconds as measured by the instrument. Results are containedin Table 1. TABLE 1 Catalyst Yield Density Mw Run (μmol) (g) Eff.¹(g/ml) (×10³) Mw/Mn MMI² 1 Ex. 2 (0.3) 18.8 1.31 0.897 <0.1 2 Ex. 4(0.3) 40.9 2.85 0.892 <10.1 3 Ex. 10 (0.15) 19.5 2.7 0.901 331 1.96 — 4Ex. 10 (0.25) 46.7 3.9 0.902 — — <0.1 A* DSAT³ (0.4) 76.1 4.0 0.897  672.23 8.9

1. A metal complex corresponding to the formula:

where M is a Group 4 metal that is in the +2, +3 or +4 formal oxidationstate; R^(A) independently each occurrence is hydrogen, or ahydrocarbyl, halohydrocarbyl, hydrocarbyloxyhydrocarbyl,dihydrocarbylaminohydrocarbyl, dihydrocarbylamino, hydrocarbyloxy,hydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl group of from 1 to80 atoms, not counting hydrogen, or further optionally, two or moreR^(A) groups may be covalently linked together; Z is (R^(D))₂Si=,wherein R^(D) independently each occurrence is C₇₋₂₀ alkaryl or twoR^(D) groups together are alkyl- or polyalkyl-substituted arylene of upto 40 carbons; and Y is bonded to M and Z and is selected from the groupconsisting of —O—, —S—, —NR and —PR^(E)—; wherein, R^(E) independentlyeach occurrence is hydrogen, or a member selected from hydrocarbyl,hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, andcombinations thereof, said R^(E) having up to 20 nonhydrogen atoms X isan anionic or dianionic ligand group having up to 60 atoms exclusive ofthe class of ligands that are cyclic, delocalized, π-bound ligandgroups; X′ independently each occurrence is a neutral ligand having upto 40 atoms; p is zero, 1 or 2, and is two less than the formaloxidation state of M when X is an anionic ligand, and when X is adianionic ligand group, p is 1; and q is zero, 1 or 2:
 2. A metalcomplex according to claim 1, corresponding to the formula:

where R^(B′) corresponds to the formula N(R^(B))₂, wherein R^(B) eachoccurrence is C₁₋₁₀ hydrocarbyl, or a halo- or tri(C₁₋₄hydrocarbyl)silyl-substituted derivative thereof, or two R^(B) groupstogether form a divalent hydrocarbon moiety, or a halo- or tri(C₁₋₄hydrocarbyl)silyl-substituted derivative thereof, said divalent groupcontaining from 4 to 40 atoms not counting hydrogen; and R^(A), Z, M, X,X′, p and q are as previously defined. wherein —N(R^(B))₂, isdibenzylamino or two R^(B) groups together with the nitrogen atom form acycloaliphatic group, and at least one of the A^(R) groups comprisingR^(B) is a single or multiple ring, aromatic group.
 3. A metal complexaccording to claim 1, wherein —N(R^(B))₂ is in the form of a multiplering, fused, aza-cyclic group.
 4. A metal complex according to claim 1,wherein —N(R^(B))₂ is 1,3-dihydro-2H-isoindol-2-yl,1,2,3,4-tetrahydro-2H-isoquinoline-2-yl,1,3-dihydro-2H-benzo[f]isoindol-2-yl,1,3-dihydro-2H-benzo[e]isoindol-2-yl,1,2,3,4-tetrahydro-2H-benzo[g]isoquinoline-2-yl,1,2,3,4-tetrahydro-2H-benzo[f]isoquinoline-2-yl,1,2,3,4-tetrahydro-2H-benzo[h]isoquinoline-2-yl, 1H-benzo[de]isoquinolin-2(3H)-yl, or dibenzylamino,
 5. A metal complexaccording to claim 1 corresponding to the formula:

where R^(F) is C₁₋₁₀ alkyl substituted phenyl, preferably C₄-₁₀ alkylsubstituted phenyl, most preferably n-butylphenyl, most highlypreferably para-n-butylphenyl; R^(I) is chloro, methyl, benzyl,trimethylsilylmethyl or two R^(I) groups together are(dimethylsilylene)bis(methylene); and R^(J) is allyl,2-(dimethylamino)benzyl, 1,4-pentadiene or 1,4-diphenyl-1,3-butadiene.6. A compound according to claim 1 selected from the group consistingof:dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;dichloro(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(cyclohexyl)-1,l-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-1-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N)-titanium(II) 1,4-diphenyl-1,3-butadiene;dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III) 2-(N,N-dimethylamino)benzyl;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,4-diphenyl-1,3-butadiene;dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III)2-(N,N-dimethylamino)benzyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II)1,4-diphenyl-1,3-butadiene;dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III)2-(N,N-dimethylamino)benzyl;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II)1,4-diphenyl-1,3-butadiene;dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III)2-(N,N-dimethylamino)benzyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II)1,4-diphenyl-1,3-butadiene;dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III)2-(N,N-dimethylamino)benzyl;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II)1,4-diphenyl-1,3-butadiene;dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl))-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III)2-(N,N-dimethylamino)benzyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II)1,4-diphenyl-1,3-butadiene;dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III)2-(N,N-dimethylamino)benzyl;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II)1,4-diphenyl-1,3-butadiene;dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III)2-(N,N-dimethylamino)benzyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II)1,4-diphenyl-1,3-butadiene;dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III)2-(N,N-dimethylamino)benzyl;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II)1,4-diphenyl-1,3-butadiene;dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III)2-(N,N-dimethylamino)benzyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II)1,4-diphenyl-1,3-butadiene;dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III)2-(N,N-dimethylamino)benzyl;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II)1,4-diphenyl-1,3-butadiene;dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)iphenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III)2-(N,N-dimethylamino)benzyl;(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-indene-1-yl)silanaminato-(2-)-N-)-titanium(II)1,4-diphenyl-1,3-butadiene;dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumbis(trimethylsilylmethyl);N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(dimethylsilylene)bis(methylene);(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(III)2-(N,N-dimethylamino)benzyl; and(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II)1,4-diphenyl-1,3-butadiene.
 7. A catalyst composition comprising (A) themetal complex of claims 1-6 and (B) an activating cocatalyst, or areaction product thereof, wherein the molar ratio of (A) to (B) is from1:10,000 to 100:1.
 8. A process for polymerizing one or more additionpolymerizable monomers, comprising contacting said monomer or a mixtureof such monomers under polymerization conditions with a catalystcomposition according to claim 7.